2-methylbutylbenzene

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenylmagnesium bromide solution repapred from 40 g of bromobenzene, 6.2 g of magnesium and 300 ml of ether was cooled at 5° C., and a mixture liquid of 125 g of 2'-methylbutyl 4-methylbenzenesulfonate (II) prepared above and 130 ml of ether was added dropwise. After 2 hours of stirring, the mixture was elevated in temperature to effect 2 hours of refluxing, followed by standing overnight. To the reaction liquid, 10 % H2SO4 was added with pH 2. The organic layer was washed successively with an aqueous sodium bicarbonate solution and water, followed by drying with anhydrous magnesium sulfate, and distilling-off of the solvent. The product was distilled under reduced pressure to obtain 48 g of 4-(2'-methylbutyl)benzene (III) which showed the following IR data: was added dropwise to effect 2 hours of refluxing by standing overnight was added with pH 2 The organic layer was washed successively with an aqueous sodium bicarbonate solution and water by drying with anhydrous magnesium sulfate The product was distilled under reduced pressure

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenylmagnesium bromide solution repapred from 40 g of bromobenzene, 6.2 g of magnesium and 300 ml of ether was cooled at 5° C., and a mixture liquid of 125 g of 2'-methylbutyl 4-methylbenzenesulfonate (II) prepared above and 130 ml of ether was added dropwise. After 2 hours of stirring, the mixture was elevated in temperature to effect 2 hours of refluxing, followed by standing overnight. To the reaction liquid, 10 % H2SO4 was added with pH 2. The organic layer was washed successively with an aqueous sodium bicarbonate solution and water, followed by drying with anhydrous magnesium sulfate, and distilling-off of the solvent. The product was distilled under reduced pressure to obtain 48 g of 4-(2'-methylbutyl)benzene (III) which showed the following IR data: was added dropwise to effect 2 hours of refluxing by standing overnight was added with pH 2 The organic layer was washed successively with an aqueous sodium bicarbonate solution and water by drying with anhydrous magnesium sulfate The product was distilled under reduced pressure

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (+)-2-Methylbutylbenzene, prepared according to the procedure of Example 2, (0.75 mol, 111.0 gm) was added to 200 ml glacial acetic acid. This solution was added dropwise to a mixture of 420 ml 90% fuming nitric acid and 180 ml glacial acetic acid, which had been cooled at -20° C. Maintaining that temperature, the mixture was stirred for one hour and then poured into 2.5 l of ice water. The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) and the combined extracts were successively washed with water (2-100 ml portions); 5% sodium hydroxide (2-100 ml portions), 10% sodium hydroxide (2-100 ml portions); and water (3-100 ml portions). The extract was dried over anhydrous calcium sulfate, the solvent was removed under reduced pressure and the resultant light yellow oil fractionated under reduced pressure. The fraction boiling at 158°-160° C. (14 mm Hg) was collected, giving a 38% yield of the product. The structure was confirmed by NMR. This solution was added dropwise to a mixture of 420 ml 90% Maintaining that temperature The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) the combined extracts were successively washed with water (2-100 ml portions) The extract was dried over anhydrous calcium sulfate the solvent was removed under reduced pressure The fraction boiling at 158°-160° C. (14 mm Hg) was collected

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (+)-2-Methylbutylbenzene, prepared according to the procedure of Example 2, (0.75 mol, 111.0 gm) was added to 200 ml glacial acetic acid. This solution was added dropwise to a mixture of 420 ml 90% fuming nitric acid and 180 ml glacial acetic acid, which had been cooled at -20° C. Maintaining that temperature, the mixture was stirred for one hour and then poured into 2.5 l of ice water. The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) and the combined extracts were successively washed with water (2-100 ml portions); 5% sodium hydroxide (2-100 ml portions), 10% sodium hydroxide (2-100 ml portions); and water (3-100 ml portions). The extract was dried over anhydrous calcium sulfate, the solvent was removed under reduced pressure and the resultant light yellow oil fractionated under reduced pressure. The fraction boiling at 158°-160° C. (14 mm Hg) was collected, giving a 38% yield of the product. The structure was confirmed by NMR. This solution was added dropwise to a mixture of 420 ml 90% Maintaining that temperature The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) the combined extracts were successively washed with water (2-100 ml portions) The extract was dried over anhydrous calcium sulfate the solvent was removed under reduced pressure The fraction boiling at 158°-160° C. (14 mm Hg) was collected

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of the nickel catalyst prepared in step (a) (208 gm, 0.39 mmol), chlorobenzene (135 mmol) and ether (50 ml) was added (+)-2-methylbutyl magnesium bromide (60 mmol), prepared in step (b), in 50 ml ether. The mixture was kept at 0° C., with stirring, over 10 minutes. The resulting mixture was heated to reflux for 20 hr. The reactants were cooled to 20° C. and 10% hydrochloric acid was added to hydrolyze the mixture. Sodium chloride is added to saturate the aqueous layer and the water phase was extracted with 3-50 ml portions of ether. The combined extracts are washed with water, dried over calcium chloride, and concentrated in vacuo. The residue was distilled under reduced pressure and the product, which boiled at 91° C. (25 mm Hg), was collected. The structure of the product was confirmed by NMR. was kept at 0° C. The resulting mixture was heated to reflux for 20 hr to saturate the aqueous layer the water phase was extracted with 3-50 ml portions of ether The combined extracts are washed with water dried over calcium chloride concentrated in vacuo The residue was distilled under reduced pressure the product, which boiled at 91° C. (25 mm Hg), was collected

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Phenylmagnesium bromide-ether solution was prepared from bromobenzene (64.5g, 0.41m), magnesium turnings (9.85g, 0.41m), and anhydrous ether (500ml). The reagent was cooled and (+)-β-methylbutyl-4-toluenesulfonate (200g, 0.82m) in ether (800ml) was added in drops. When the addition was complete, the reaction mixture was stirred for two hours, refluxed for two hours and left to stand overnight. Aqueous sulfuric acid was added until a clear solution was formed. The layers were separated. The aqueous layer was extracted with ether (3×250ml), and the combined organic layers were washed with sodium bicarbonate solution, water and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was steam-distilled. Fractional distillation of the crude product at reduced pressure yielded (+)-β-methylbutylbenzene (38.7g, 64.8%), bp. 74°-77° C at 12 mm pressure. The reagent was cooled When the addition refluxed for two hours left to stand overnight was formed The layers were separated The aqueous layer was extracted with ether (3×250ml) the combined organic layers were washed with sodium bicarbonate solution, water dried over anhydrous sodium sulfate The solvent was evaporated the residue was steam-distilled Fractional distillation of the crude product at reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trifluoroacetic acid (150 cc) was added to a flask containing 14.0 gm hexamethylenetetramine (HMTA). (+)2-methylbutylbenzene (14.8 gm) was then added and the mixture was refluxed for 21 hours. The deep orange mixture was distilled to remove excess trifluoroacetic acid. When about one third the volume remained, the mixture was poured into 600 ml ice water and stirred for 15 minutes. Sodium carbonate was added with stirring until the mixture was basic and the product was extracted with ether. The ether extract was washed with water and dried over sodium sulfate. The ether was removed leaving 18 gm crude (+)-4(-2-methylbutyl)benzaldehyde. This was vacuum distilled (78° C. at 0.07 mm Hg). The structure of the product was confirmed by NMR. The yield of the product was 78%. the mixture was refluxed for 21 hours The deep orange mixture was distilled to remove excess trifluoroacetic acid the mixture was poured into 600 ml ice water Sodium carbonate was added with stirring until the mixture the product was extracted with ether The ether extract was washed with water dried over sodium sulfate The ether was removed

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (+)-2-Methylbutylbenzene, prepared according to the procedure of Example 2, (0.75 mol, 111.0 gm) was added to 200 ml glacial acetic acid. This solution was added dropwise to a mixture of 420 ml 90% fuming nitric acid and 180 ml glacial acetic acid, which had been cooled at -20° C. Maintaining that temperature, the mixture was stirred for one hour and then poured into 2.5 l of ice water. The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) and the combined extracts were successively washed with water (2-100 ml portions); 5% sodium hydroxide (2-100 ml portions), 10% sodium hydroxide (2-100 ml portions); and water (3-100 ml portions). The extract was dried over anhydrous calcium sulfate, the solvent was removed under reduced pressure and the resultant light yellow oil fractionated under reduced pressure. The fraction boiling at 158°-160° C. (14 mm Hg) was collected, giving a 38% yield of the product. The structure was confirmed by NMR. This solution was added dropwise to a mixture of 420 ml 90% Maintaining that temperature The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) the combined extracts were successively washed with water (2-100 ml portions) The extract was dried over anhydrous calcium sulfate the solvent was removed under reduced pressure The fraction boiling at 158°-160° C. (14 mm Hg) was collected

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenylmagnesium bromide solution prepared from 40 g of bromobenzene, 6.2 g of magnesium and 300 ml of ether was cooled at 5° C., and a mixture liquid of 125 g of 2'-methylbutyl 4-methylbenzenesulfonate (II) prepared above and 130 ml of ether was added dropwise. After 2 hours of stirring, the mixture was elevated in temperature to effect 2 hours of refluxing, followed by standing overnight. To the reaction liquid, 10 % H2SO4 was added with pH 2. The organic layer was washed successivly with an aqueous sodium bicarbonate solution and water, followed by drying with anhydrous magnesium sulfate, and distilling-off of the solvent. The product was distilled under reduced pressure to obtain 48 g of 4-(2'-methylbutyl)benzene (III), which showed the following IR data: was added dropwise to effect 2 hours of refluxing by standing overnight was added with pH 2 The organic layer was washed successivly with an aqueous sodium bicarbonate solution and water by drying with anhydrous magnesium sulfate The product was distilled under reduced pressure

Conditions: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A phenylmagnesium bromide solution repapred from 40 g of bromobenzene, 6.2 g of magnesium and 300 ml of ether was cooled at 5° C., and a mixture liquid of 125 g of 2'-methylbutyl 4-methylbenzenesulfonate (II) prepared above and 130 ml of ether was added dropwise. After 2 hours of stirring, the mixture was elevated in temperature to effect 2 hours of refluxing, followed by standing overnight. To the reaction liquid, 10 % H2SO4 was added with pH 2. The organic layer was washed successively with an aqueous sodium bicarbonate solution and water, followed by drying with anhydrous magnesium sulfate, and distilling-off of the solvent. The product was distilled under reduced pressure to obtain 48 g of 4-(2'-methylbutyl)benzene (III) which showed the following IR data: was added dropwise to effect 2 hours of refluxing by standing overnight was added with pH 2 The organic layer was washed successively with an aqueous sodium bicarbonate solution and water by drying with anhydrous magnesium sulfate The product was distilled under reduced pressure

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (+)-2-Methylbutylbenzene, prepared according to the procedure of Example 2, (0.75 mol, 111.0 gm) was added to 200 ml glacial acetic acid. This solution was added dropwise to a mixture of 420 ml 90% fuming nitric acid and 180 ml glacial acetic acid, which had been cooled at -20° C. Maintaining that temperature, the mixture was stirred for one hour and then poured into 2.5 l of ice water. The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) and the combined extracts were successively washed with water (2-100 ml portions); 5% sodium hydroxide (2-100 ml portions), 10% sodium hydroxide (2-100 ml portions); and water (3-100 ml portions). The extract was dried over anhydrous calcium sulfate, the solvent was removed under reduced pressure and the resultant light yellow oil fractionated under reduced pressure. The fraction boiling at 158°-160° C. (14 mm Hg) was collected, giving a 38% yield of the product. The structure was confirmed by NMR. This solution was added dropwise to a mixture of 420 ml 90% Maintaining that temperature The reaction products were extracted with 2-500 ml portions of petroleum ether (30°-60° C.) the combined extracts were successively washed with water (2-100 ml portions) The extract was dried over anhydrous calcium sulfate the solvent was removed under reduced pressure The fraction boiling at 158°-160° C. (14 mm Hg) was collected

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of the nickel catalyst prepared in step (a) (208 gm, 0.39 mmol), chlorobenzene (135 mmol) and ether (50 ml) was added (+)-2-methylbutyl magnesium bromide (60 mmol), prepared in step (b), in 50 ml ether. The mixture was kept at 0° C., with stirring, over 10 minutes. The resulting mixture was heated to reflux for 20 hr. The reactants were cooled to 20° C. and 10% hydrochloric acid was added to hydrolyze the mixture. Sodium chloride is added to saturate the aqueous layer and the water phase was extracted with 3-50 ml portions of ether. The combined extracts are washed with water, dried over calcium chloride, and concentrated in vacuo. The residue was distilled under reduced pressure and the product, which boiled at 91° C. (25 mm Hg), was collected. The structure of the product was confirmed by NMR. was kept at 0° C. The resulting mixture was heated to reflux for 20 hr to saturate the aqueous layer the water phase was extracted with 3-50 ml portions of ether The combined extracts are washed with water dried over calcium chloride concentrated in vacuo The residue was distilled under reduced pressure the product, which boiled at 91° C. (25 mm Hg), was collected